Reaction products of nitreles



Patented Oct. 28, 1952 REACTION PRODUCTS F NITRILES Ernst Zerner and Mark W. Pollock, New York, N. Y., assignors to Sun Chemical Corporation, New York, N. Y., a. corporation of Delaware No Drawing. Original application June 10, 1948, Serial No. 32,263. Divided and this applicatio April 13,1951, Serial No. 220,966 I 7 claims. (01. 260-248) This invention relates to new organic materials, and is a division of our copending application, Serial No. 32,263, filed June 10, 1948.

In a copending application, Serial No. 16,135 filed March 20, 1948, there are described and claimed hexahydro-1,3,5-triacyl-s-triazine materials represented by the general formula where R represents substituted or unsubstituted open chain hydrocarbon radicals. .One of the materials described in the above identified copending application is hexahydro-1,3,5-triacrylyl-s-triazine. Also there is described in this copending application hexahydro-1,3,5-trimethacrylyl-s-triazine.

We have found according to the present invention that certain new and useful products may be obtained by proper further reactions with the latter materials.

The above derivatives of triazines contain in their molecular structure three vinyl groupings. In accordance withthe present invention derivatives are secured by reactions which lead, by the formation of addition compounds to saturation of one, two or three of the vinyl groups present. Such products may be described by the formula where R: is a radical which is selected from the group consisting of CA:CHA where A is selected from the group consisting of hydrogen, halogen and lower alkyl radicals and addition products of --CA:CI-IA and where R4115 an addition product of -CA:CI- IA.

Of these materials thosewhich contain one or two vinyl groups present-in the molecule of the products may be further treated to efiect polymerization of this material, either alone or admixed with other polymerizable monomers to furnish valuable, resinous materials which may be employed in various arts in which such materials find application, for instance, as coating materials for paper, wood, metaland cloth, in conjunction with drying oils, and the like.

The polymerized materials, described and claimed in a copending application, Serial No. 32,264, filed June 10, 1948 in the names of Ernst Zerner, Marcel Gradsten and Fred W. West, may be described as polymerization products of compounds of the general formula where R1 represents the radical --'CH:CH2 where A is selected from the group consisting of hydrogen, halogen and lower alkyl radicals where R2 is a radical selected from the group consisting of CA=CH2 and addition products of CA=CH2. I

As described in the above identified copending application Serial No. 16,135, hexahydro-1,3,5- triacrylyl-s-triazine satisfactorily may be prepared as follows: In a suitable reaction vessel provided with a stirrer, reflux condenser, thermometer and a dropping funnel are placed 265 parts by weight of acrylonitrile dissolved in 400 parts by weight of benzene, together with 2.8 parts of concentrated sulfuric acid. vIn the dropping funnel is placed a solution of parts by weight of trioxane dissolved in 400 parts by weight of benzene. The acrylonitrile solution is warmed, satisfactorily on a boiling water bath, and the material in the dropping funnel added at a rate such that the mixture is maintained under reflux condition. When all of the solution in the dropping funnel has been added, the resulting admixture is heated under reflux conditions for an additional period of approximately three hours. Subsequently the mixture,.which contains a yellow precipitate, is allowed to stand overnight and the precipitate then separated by filtration and subsequently recrystallized from ethanol.

As described in the above identified copending application, Serial No. 16,135, similar products may be obtained using as starting materials nitriles such asmethacrylonitrile, alpha chloracrylonitrile, and similar nitriles containing a vinyl group. In place of the individual nitriles, mixtures of nitrile materials can be employed.

Triazines of the above type and containing three vinyl groups may be: represented by the formula where A is hydrogen, halogen or a lower alkyl radical. Such materials may be subjected to polymerization reactionseither alone or admixed with other polymerizable monomers to form valuable resinous reaction products.

Illustrative of the preparation of such. polymer materials are the following examples.

Example I pounds having an active hydrogen, hydrogen sulfide and mercaptans.

Where the above illustrative materials," are employed to effect reaction with triazines containing vinyl groups, either one, two or three of the vinyl groups may be saturated, depending upon the. amount of reacting materials utilized.

Where only one or two of the vinyl groups is ment a polymer material is precipitated from M solution and may be separated therefrom for further utilization.

In the above preparation the rate of formation of the polymer material can be increased by utilization of a peroxide in the reaction solution.

Example II A 5 per cent solution of hexahydro-l,3,5-triacrylyl-s-triazine in chloroform together with 0.1 per cent of benzoyl peroxide, based on the triazine, is warmed to effect evaporation of the chloroform and subsequently heated for a period of approximately hour at a temperature of 130 C. in a suitable container. A brittle white, insoluble polymer material is secured.

Polymerization of such materials may also be efiected, for example, in the presence of a textile material in which case a product is obtained which comprises the textile material impregnated with the resinous product.

Also, as above set forth, copolyinerization may be effected, as illustratively set forth in the following example,

Example III A mixture containing 99,65 per cent by Weight of styrene, 0.25 per cent by weight of hexahydro- 1,3,5-triacrylyl-s-triazine and 0.1 per cent of benzoyl peroxide is heated to 60 C. to eifect formation of a polymer material. The rate of polymerization is much more rapid with the triazine present than in its absence, and the product obtained is a crosslinked 'polymen'as distinguished from linear polymers which are obtained by the polymerization of styrene. Evidence for this is the fact that the copolymerization product is insoluble in xylol, whereas poly per mol of triazine.

thus saturated, the resulting material may be polymerized, either alone or in conjunction with other p'olymerizable monomers to form a resinous product, whose characteristics will be de pendent in part upon the modifying reacting material employed to eiiect saturation of the vinyl groupings prior to polymerization, as described and claimed in the said copending application Serial No. 32,264.

Illustrative examples setting forth this aspect include the following.

Example IV 20 parts by weight of heXahydro-1,3,5-triacrylyl-s-triazine is'dissolved in 500 parts of water at approximately 75 C. When solution is completed there is added thereto 8.2 parts by weight of sodium bisulfite which corresponds to one molecular equivalent of sodium bisulfite per mol of triazine. Addition of the bisulfite is effected while maintaining the solution under agitation conditions. When addition of the bisulfite is completed the admixture is cooled and may be filtered to remove traces of impurities. A slightly milky solution results. Upon drying of this solution under vacuum conditions, there is obtained-aiclear white solid which is easily soluble in water and which does not melt or decom- 7 Example V Aqueous solutions of the product of Example IV, upon treatment with 30 per cent hydrogen peroxide solution polymerized to give a resinous product.

- Example VI A 5-6 per cent solution of the product of Example IV in water, together with two drops of 30 per cent-hydrogen peroxide per parts by Weight of solution was heated at boiling for ten minutes. The resulting solution was cooled and was employed in normal padding operation to effect impregnation of percale. After padding was completed, the impregnated percale was dried at 100 C. The treated material'was remarkably stiffer than the original untreated goods, such effect being caused by the polymerization of the sodium bisulfite addition product of hexahydro-1,3,5-triacrylyl-s-triazine in situ in the fabric material.

Example VII 20 parts by weight of hexahydro-l,3,5-triacrylyl-s-triazine is dissolved in 500 parts by weight of water at '75 C. When solution is completed there is added, with agitation, 16.4 parts by weight of sodium bisulfite corresponding to two molecular equivalents of sodium bisulfite After addition of the bisulfite is--completed, the admixture is cooled and filtered to remove impurities. Upon drying of the filtrate under vacuum condition, a clear white water-soluble product is secured which does not melt at temperatures up to 250 C.

Example VIII Polymerization of the product of Example VII "5 is obtained by dissolving" thepr'oduct in water and treating the aqueous solution with 30 per "cent hydrogen peroxide.

Example IX parts by weight of hexahydro-1,-3,5 -triacrylyl-s-triazine is dissolved, in 200 parts of chloroform in a reaction vessel equipped ,-with stirring device, thermometer, dropping funnel and reflux condenser. There is then added drop-wise a solution of 0.4 part by weight of metallic sodium dissolved in 12 parts of n-butanol. Upon completion of this addition the admixture is stirred for a length of time sufficient to complete the reaction, which with the quantities above described is approximately 8 hours. At the endof this reaction period the mixture is madeacidic by addition of glacial aceticacid thereto;- .The reaction admixture is then diluted with l times its volume of ether and filtered. The filtrate is evaporated to remove ether and chloroform and the residue washed with water and then dissolved in ether. The ether solution is dried, satisfactorily with sodium sulfate, and then filtered. To

remove ether the admixture is distilled under reduced pressure. A brownvi'scous oil, the butyl alcohol addition product of 'heXahydro-1,3,5-triacrylyl-s-triazine is obtained.

The product, upon heating'together with benzoyl peroxide, forms a resinous product.

Hexahydro-1,3,5-triacry1yl-s-triazine may be chlorinated by bubbling chlorine into the material in the presence of a small amount of a polymerization inhibitor such as hydroquinone in an amount sufficient to effect saturation of one, two or three of the vinyl groups present. .The source of the reaction may be'deterrrfined by the in.- crease in weight of the reaction admixture at intervals. Where chlorination is discontinued at a point where less than all of the vinyl groups are saturated, a product is obtained which may be polymerized. Polymerization satisfactorily is effected in the presence of a peroxide polymerization catalyst.

Example X'I Example XII In a suitable reaction vessel were placed 50 parts of chloroform and 12.5 parts by weight of hexahydro-1,3,5-triacrylyl-s-triazine. The mixture is warmed until solution is completed, then cooled to room temperature and there is then added thereto, in small portions, 8 parts by weight .6 of decylfamine at a iate"such*that the temperature of thefadmixtureidoes'not" rise' above approximately 37 C. After addition of the amine is completed, the reaction admixture is stirred for a period" of time sufficient to insure completion of the reactionwhicli'with the quantities ab'ove described isapproximately'125 hours. The mixture then may be; allowed" to stand for several hours and subsequently is filtered and the chloroform removed ther'efrom by distillation under re- 'duced pressure. A'clear viscous liquid material is obtained.' I Example XIII V Polymerization of the product of Example XII may be secured-either in the presence of a peroxide oxidation catalyst or, in the absence-ofa catalyst, over a somewhat longer period of time. The product which is obtained by polymerization is insoluble in ordinary organic solvents indicating that the process of: polymerization includes cross-linking of the polymers and that the product is not a simple linear polymer.

Example XIiV Following the procedure described in Example XII and utilizing 16 parts by weight of decyl amine there is secured an addition product in which two of the three vinyl groups of the triazines' have'zbleensaturated.1 This product polymerizes ata rate, slower than the product of Example XIII and serves satisfactorily as a plasticizing polymer to be used in conjunction with the polymer of Example XIII.

Example XV In a reaction vessel are placed parts of chloroform and 12.5 parts by weight of hexahydro-1,3,5-triacrylyl-s-triazine and there is then added thereto with stirring 3.65 parts by weight of diethyl amine dissolved in 10 parts of chloroform. After agitation is completed, the admixture is stirred for approximately 2 hours, stirring then discontinued and the mixture allowed to stand forseveral hours- It then is filtered and Exam le XVI" The procedure described in Example XV is followednexcept.that there is used v8 parts .by weight .of diethyl amine to give. a product which is an addition product containing two molecular equivalents of diethyl amine per mol of triazine. The product is water-soluble and is a surface active material.

Ewample XVII The procedure described in Example XV is followed except thatthere' is utilized 12 parts by weight of diethylamine to give-a reaction product containing three molecular equivalents of diethyl ami'ne per mol of triazins Products in which the triazines of the present invention are reacted with materials containing an activehydrogenisuch asz-fiuorenermay' berpfg- 8 pared by the utilization of alkaline condensing 4. As a new product, a compound of the foragents. Illustrations of such reactions involving mule, V nitrile materials are set forth in U. S. Patent No. GB 2,280,058 of April 21,1942.- u

Illustrations of reaction conditions which may be employed to effect saturation of the, vinyl 1 groups of triazines of the present invention with I materials such as hydrogen sulfide are set forth in U. S. Patent No. 2,163,176 dated June 20, 1939. H29 CH1 While the above described products constitute H O O H preferred embodiments of the invention, changes I l! H may be made therein without departing from the X CHZ C N\ N C- CH Y scope of the invention, as defined in the ap- Cl pended claims. a

What is claimed is: where Y represents an amino-alkyl radical. 1. As a new product, a compound of the for- 5. As a new product, a compound of the formula mula on, U CH2 F ("3H o=o 1 (3:0 1' HzC CH2 Q I HzC CH2 A o o A H H I C2H5 O O C2H5 YCH1-CCN N-C-CCH-.-Y H H I I N-CH:-CHr-CN C-CH2CHz-N H c 11 .H; CzHs g C2115 where A is selected from the group consisting of hydrogen, halogen and lower alkyl radicals, and AS a new p c a p d of the forwhere Y is selected from the group consisting of mula SOs-alkali metal, oxy-alkyl and amino-alkyl '7. As a new product, a compound of the forradicals. mula 2. As a newproduct, a compound of the for- CH2 mula y (A H 17 0 on 59 l i Hi0 CH: N l o H fl CH2 II M NaSOr-CHz-GH:G-N /NCCH2CHrSOaNa v C V YCHz-CHz- -N\ /NP3CHr-CH7Y I H: G ERNST ZERNER. H3 MARK W. POLLOCK. where Y represents an amino-alkyl radical.

3. As a new product, a compound of the for- 1 I REFERENCES CITED mula, The following references are of record in the CH: file of this patent: (L0H V UNITED STATES PATENTS I a 0:0 Number Name Date i 2,559,835 Zerner July 10, 1951 2,568,620 Gresham Sept. 18, 1951 H30 CH7 i if I w r Y-CHz-(l)-C-N\ N-C-C-CH:-Y

CH; 0 CH;

where Y represents an amino-alkyl'radic'al; Y 7 

1. AS A NEW PRODUCT, A COMPOUND OF THE FORMULA 